Simulating speleothem growth in the laboratory: Determination of the stable isotope fractionation (δ13C and δ18O) between H2O, DIC and CaCO3

Here we present novel cave-analogue experiments directly investigating stable carbon and oxygen isotope fractionation between the major involved species of the carbonate system (HCO3-,CO2, CaCO3 and H2O). In these experiments, which were performed under controlled conditions inside a climate box, a thin film of solution flew down an inclined marble or glass plate. After different distances of flow and, thus, residence times on the plate, pH, electrical conductivity, supersaturation with respect to calcite, precipitation rate as well as the delta O-18 and delta C-13 values of the dissolved inorganic carbon (DIC) and the precipitated CaCO3 were obtained. Progressive precipitation of CaCO3 along the plate is accompanied by degassing of CO2 and stable isotope fractionation, and the system is driven out of isotope equilibrium. We observe a strong enrichment of the delta C-13 values with increasing residence time and a smaller enrichment in delta O-18. The temporal evolution of the delta O-18 and delta C-13 values of both the DIC and the precipitated CaCO3 can be explained by a Rayleigh fractionation model, but the observed enrichment in delta C-13 values is much larger than expected based on isotope equilibrium fractionation factors. Our setup enables to determine the fractionation between CaCO3 and HCO3-,i.e., epsilon(CaCO3/HCO3-).Carbon isotope fractionation, (13)epsilon(CaCO3/HCO3-), is strongly negative for all experiments and much lower than equilibrium isotope fractionation (0-1 parts per thousand). In addition,(13)epsilon(CaCO3/HCO3- )decreases with increasing residence time on the plate, and thus decreasing supersaturation with respect to calcite. Thus, isotope fractionation depends on precipitation rate and consequently occurs under kinetic conditions. This is in contrast to previous studies, which found no rate-dependence and no or even a positive carbon isotope fractionation between CaCO3 and HCO3. Oxygen isotope fractionation, (18)epsilon(CaCO3/HCO3-), is also negative and dependent on precipitation rate. Since no literature values for (18)epsilon(CaCO3/HCO3-) are available, we calculated (18)epsilon(CaCO3/HCO3-) using equilibrium oxygen isotope fractionation factors between water and calcite and water and HCO3, respectively. At the beginning of the plate, the fractionation is in agreement with the fractionation calculated using fractionation factors determined in cave systems. The observed fractionation between CaCO3 and water, 1000ln(18)alpha, is also in good agreement with the values determined in cave systems and shows a very similar temperature dependence 1000/ln(18)alpha = 16.516(+/- 1.267) * 10(3)/T - 26.141(+/- 4.356). However, with progressive precipitation of CaCO3 along the plate, the system is forced out of isotope equilibrium with the water, and 1000ln (18)alpha increases. The large, negative, rate-dependent isotope fractionations observed in this study suggest that precipitation of speleothem calcite is strongly kinetically controlled and may, thus, have a large effect on speleothem delta O-18 and delta C-13 values. Since these values may erroneously be interpreted as reflecting changes in past temperature, precipitation and/or vegetation density, these results have important implications for paleoclimate reconstructions from speleothems.